US5015469A - Water-in-oil emulsion type cosmetics - Google Patents

Water-in-oil emulsion type cosmetics Download PDF

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US5015469A
US5015469A US07/560,486 US56048690A US5015469A US 5015469 A US5015469 A US 5015469A US 56048690 A US56048690 A US 56048690A US 5015469 A US5015469 A US 5015469A
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water
oil
weight
clay mineral
polyoxyalkylene modified
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Toshio Yoneyama
Michihiro Yamaguchi
Shinji Tobe
Tomiyuki Nanba
Masaaki Ishiwatari
Hidekazu Toyoda
Shin Nakamura
Yoshimaru Kumano
Sadaki Takata
Hiromi Ito
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Shideido Co Ltd
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Shideido Co Ltd
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26—Aluminium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/416—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments

Definitions

  • the present invention relates to a water-in-oil type (hereinafter abbreviated as W/O type) emulsified composition useful as a cosmetic or ointment base. More specifically, it relates to a water-in-oil type emulsified composition having specific features whereby a range of oils from polar oils to non-polar oils can be widely employed as the oil component which becomes the outer phase and the emulsified composition obtained has an excellent temperature stability and usability.
  • W/O type water-in-oil type emulsified composition useful as a cosmetic or ointment base. More specifically, it relates to a water-in-oil type emulsified composition having specific features whereby a range of oils from polar oils to non-polar oils can be widely employed as the oil component which becomes the outer phase and the emulsified composition obtained has an excellent temperature stability and usability.
  • the present invention also relates to a water-and polyhydric alcohol-in-oil type emulsified composition useful as a cosmetic or ointment base. More specifically, it relates to a water- and polyhydric alcohol-in-oil type emulsified composition having specific features whereby a silicone oil can be used as the oil component which becomes the outer phase, and the emulsified composition obtained has an excellent temperature stability.
  • the composition is not referred to as a water-in-oil type emulsified composition or polyhydric alcohol-in-oil type emulsified composition, because the inner phase of this emulsion composition comprising the main component exists in the region bridging the region of water and the region of polyhydric alcohol, and therefore, neither expression is adequate.
  • water- and polyhydric alcohol-in-oil type emulsified composition denotes an emulsified composition containing both water and a polyhydric alcohol in the oil phase.
  • a lipophilic surfactant having a HLB value of 1 to 12 for example, a polyhydric alcohol fatty acid ester type surfactant such as glycerine fatty acid ester, sorbitan fatty acid ester, etc.
  • this surfactant is added in an amount of about 0.4 to 5.0 g into the oil phase, to be dissolved therein by heating to about 70° to 80° C., and the aqueous phase heated to about the same temperature is then added, followed by stirring by a homomixer, etc., to obtain a W/O type emulsified composition (hereinafter called W/O type emulsion).
  • the W/O type emulsion thus obtained has a drawback in that a system having an excellent temperature stability and usability can be obtained only with difficulty, compared with the oil-in-water type (hereinafter called O/W type) emulsion.
  • O/W type oil-in-water type
  • a separation of the oil phase which is the continuous phase, may occur due to an agglomeration of water droplets at a low temperature.
  • This oil phase separation also occurs at a high temperature, in that water droplets are combined, and thus have an increased particle size, and precipitated to form a sediment lower layer, and thus the upper layer consists of only the oil phase.
  • the outer phase consists of an oil component, the advantages of skin protection, flexibility, etc., can be obtained in the fields of cosmetics and pharmaceuticals, although the drawbacks of stickiness during usage and a high skin barrier also exist.
  • a polar oil component having ester bond as widely employed in the O/W type emulsion system, is formulated, but when the W/O type emulsifier used in the prior art is formulated, it is difficult to form a W/O type emulsion having an excellent stability in a system wherein a polar oil component is also formulated.
  • the objects of the present invention are to eliminate the above-mentioned disadvantages of the prior art and to provide a water-in-oil type emulsified composition capable of being widely employed as an oil component and having an excellent temperature stability and usability.
  • Another object of the present invention is to provide a water- and polyhydric alcohol-in-oil type emulsified composition capable of being employed as an oil component and having an excellent temperature stability.
  • a water-in-oil type emulsified composition comprising, a water-swellable clay mineral, a nonionic surfactant, an oil component, and water, as the essential constituents.
  • a water-in-oil type emulsified composition comprising, a water-swellable clay mineral, a quaternary ammonium salt type cationic surfactant, one or two or more kinds of polyoxyalkylene modified organopolysiloxane, an aqueous phase, and an oil phase containing one or two or more kinds of an organic silicone resin comprising the units of the formula:
  • R is a hydrocarbon group having 1 to 6 carbon atoms or a phenyl group, and n represents a value of 1.0 to 1.8.
  • a water- and polyhydric alcohol-in-oil type emulsified composition comprising an oil component containing a silicone oil using a polyoxyalkylene modified organopolysiloxane, a water-swellable clay mineral, a quaternary ammonium salt type cationic surfactant water, and a polyhydric alcohol.
  • FIG. 1 shows the relationship between the amounts formulated and viscosity of Smectite.
  • the axis of the ordinate represents the viscosity (cps)
  • the axis of the abscissa shows the % by weight of Smectite.
  • the water-swellable clay minerals to be used in the present invention are laminar silicate minerals belonging to genus Smectite generally including montmorillonite, beidelite, nontronite, saponite, hectorite, etc. These may be natural or synthetic.
  • Examples of the commercially available products are Kunipia, Smecton (both from Kunipia Kogyo), Veegum (from Vanderbilt Co.), Laponite (from Laporte Co.), fluorine tetra silicic mica (from Topy Kogyo K.K.).
  • Kunipia Smecton
  • Veegum from Vanderbilt Co.
  • Laponite from Laporte Co.
  • fluorine tetra silicic mica from Topy Kogyo K.K.
  • one or more kinds of minerals are used from these water-swellable clay minerals.
  • the formulated amount is suitably 0.2 to 5.0% by weight, more preferably 0.2 to 3.0% by weight, based on the total weight of the emulsified composition of the present invention. If the proportion is less than 0.2% by weight, the temperature stability may not be satisfactory, depending on the product, and if formulated in excess of 5.0% by weight, the viscosity of the system may be increased, which may have an adverse affect on the usability of some product.
  • nonionic surfactants having an HLB value of 2 to 16, more preferably 3 to 12 may be included.
  • the HLB value of the nonionic surfactant is calculated by the Kawakami formula shown below: ##EQU1## (wherein Mw represents the molecular weight of the hydrophilic group portion, and Mo represents the molecular weight of the lipophilic group portion.)
  • ethylene oxide addition type surfactants including ether type surfactants such as polyoxyethylene 2-30 mole addition [hereinafter abbreviated as POE (2-30)]oleyl ether, POE (2-35) stearyl ether, POE (2-20) lauryl ether, POE (1-20) alkylphenyl ether, POE (6-18) behenyl ether, POE (5-25) 2-decylpentadecyl ether, POE (3-30) 2-decyltetradecyl ether, POE (8-16) 2-octyldecyl ether, etc.; ester type surfactants such as POE (4-60) hardened castor oil, POE (3-14) fatty acid monoester, POE (6-30) fatty acid diester, POE (5-20) sorbitan fatty acid ester, etc.; ether ester type surfactants such as POE (2-30) glyceryl monoisostearate, POE (10-60) glyceryl monois
  • nonionic surfactants such as polyglycerine fatty acid esters of triglycerine or higher such as decaglyceryl tetraoleate, hexaglyceryl triisostearate, tetraglyceryl diisostearate, POE addition ether type surfactants such as POE (2-12) oleyl ether, POE (3-12) stearyl ether, POE (2-10) lauryl ether, POE (2-10) nonylphenyl ether, POE (6-15) behenyl ether, POE (5-20) 2-decylpentadecyl ether, POE (5-17) 2-decyltetradecyl ether, and POE (8-16) 2-octyldecyl ether, etc.; POE addition ester type surfactants such as POE (10-20) hardened castor oil, POE (5-14) oleic acid monoester, POE (6-20) oleic
  • nonionic surfactants there may be included polyether modified silicone compounds represented by the following formulae. Note, these surfactants are particularly suitable when the oil is a silicone oil or an oil containing a silicone oil. ##STR1##
  • one or two or more kinds may be selected and used as desired from among these nonionic surfactants.
  • the amount formulated is preferably 0.05 to 2-fold relative to the water-swellable clay mineral.
  • oil component to be used in the first aspect of the present invention all of the oil components generally employed in cosmetics, pharmaceuticals, etc., can be used, and the range of from polar oils to non-polar oils can be widely used as the oil.
  • oil component include hydrocarbon oils such as liquid paraffin, squalane, isoparaffin, branched chain light paraffin, etc.; ester oils such as isopropyl myristate, cetyl isooctanoate, glyceryl trioctanoate, etc.; silicone oils such as octamethyltetrasiloxane, decamethylcyclopentasiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, etc.
  • waxes such as petrolatum, microcrystalline, lanolin, beeswax, etc.
  • oil components are formulated in amounts of about 5 to 90% by weight, preferably 10 to 80% by weight, in the W/O type emulsion.
  • the quaternary salt type cationic surfactant to be used in the second aspect of the present invention is represented by the following formula: ##STR2## wherein R 1 is an alkyl group having 10 to 22 carbon atoms or a benzyl group, R 2 is a methyl group or an alkyl group having 10 to 22 carbon atoms, R 3 and R 4 are each an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom or a methyl sulfate residue.
  • dodecyltrimethylammonium chloride myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, arachyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethylethylammonium chloride, arachyldimethylethylammonium chloride, behenyldimethylethylammonium chloride, myristyldiethylmethylammonium chloride, cetyldiethylmethylammonium chloride, stearyldiethylmethylammonium chloride, arachyldiethylmethylammonium chloride, behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, myristy
  • one or more kinds of these surfactants may be selected as desired.
  • the content of the quaternary ammonium salt type cationic surfactant in the W/O type emulsion of the present invention is preferably 40 to 140 milliequivalents (hereinafter abbreviated as meq) more preferably 60 to 120 meq, per 100 g of the water-swellable clay mineral.
  • the quaternary ammonium salt type cationic surfactant and the water-swellable clay mineral may be added separately to the oil phase and the aqueous phase, respectively, during the preparation of the emulsion, or alternatively both, including a commercial product (e.g., Benton, produced by the National Lead Co.) may be previously allowed to react in a suitable solvent, and the reaction product may be added to the oil phase.
  • a commercial product e.g., Benton, produced by the National Lead Co.
  • the polyoxyalkylene modified organopolysiloxane to be used in the second aspect of the present invention is preferably a polyoxyalkylene modified organopolysiloxane represented by the formulae (A), (B), (C), and (D) shown above, and any one or two or more kinds thereof may be formulated; the formulated amount being preferably 75 to 2000 g, more preferably 100 to 1500 g, based on 100 g of the water-swellable clay mineral.
  • the organic silicone resin to be used in the second aspect of the present invention comprises a suitable combination of the R 3 SiO 1/2 k units, R 2 SiO units, RSiO 3/2 units and SiO 2 units, and the proportion thereof is selected so as to satisfy the average formula: RnSiO.sub.(4-n)/2 (R represents a hydrocarbon having 1 to 6 carbon atoms or a phenyl group, and n represents a value of 1.0 to 1.8), and desirably has an average molecular weight of about 1500 to 10000.
  • the amount of the organic silicone resin formulated in the present invention is 0.5 to 50% by weight in the emulsion composition, preferably 1 to 30% by weight. If less than 0.5% by weight, sufficient hardening cannot be obtained, and if over 50% by weight, the compatibility thereof with other oil components may be lowered, and the stickiness increased.
  • the polyoxyalkylene modified organopolysiloxane to be used in the third aspect of the present invention are those described above.
  • the water-swellable clay minerals to be used in the third aspect of the present invention are those as described above.
  • the quaternary salt type cationic surfactants to be used in the third aspect of the present invention are those as mentioned above.
  • the amounts of polyoxyalkylene modified organopolysiloxane, the water-swellable clay mineral, and the quaternary ammonium salt type cationic surfactant to be used in the third aspect of the present invention are controlled in accordance with the inner phase ratio and the viscosity of the emulsified composition to be obtained. Since the polyoxyalkylene modified organopolysiloxane participates in the emulsifiability, if the amount is too small, the emulsifiability is lowered, and the water-swellable clay mineral and the quaternary ammonium salt type cationic surfactant tend to raise the viscosity as the amounts formulated thereof are increased.
  • the amounts of polyoxyalkylene modified organopolysiloxane, the water-swellable clay mineral and the quaternary ammonium salt type cationic surfactant formulated are preferably 0.5 to 20% by weight, 0.1 to 5% by weight, and 0.1 to 2% by weight, respectively.
  • any of those conventionally used for cosmetics or pharmaceuticals may be used, as exemplified by dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher fatty acid modified organopolysiloxane, higher alcohol modified organopolysiloxane, trimethylsiloxy silicate, etc.
  • volatile dimethylpolysiloxane and dimethylcyclopolysiloxane having the structures (E) and (F) shown below can be exemplified, and one or more kinds thereof may be selected and used as desired.
  • the amount of the silicone oil formulated is related to the amount of the other oil phase components. If the amount of silicone oil is small, the properties of the oil phase become almost the same as the properties of the other formulated oil components, and thus a lipophilic surfactant suitable for the oil phase is preferably used. On the other hand, if the amount of silicone oil is high, the polyoxyalkylene modified organopolysiloxane of the present invention suitable for a silicone oil is preferably used. Accordingly, it is particularly preferred that the silicone oil comprise 50% or more of the oil phase component. ##STR3##
  • the polyhydric alcohol to be used in the third aspect of the present invention has 2 or more hydroxyl groups in the molecule, and includes, for example, liquid polyhydric alcohols such as polyethylene glycol, dipropylene glycol, 1,3-butylene glycol, propylene glycol, glycerine, etc., and solid polyhydric alcohols such as sorbitol, maltitol, etc.
  • the oil component is silicone oil alone, a region giving a certain transparency appears, whereby a specific appearance feature can be imparted.
  • the total amount of water and the polyhydric alcohol formulated may be about 5 to 80% by weight in the water- and polyhydric alcohol-in-oil type emulsified composition, preferably 10 to 70% by weight.
  • W/O type emulsion according to the first aspect of the present invention, it is also possible to formulate amino acids and salts thereof, humectants, thickeners, preservatives, antioxidants, sequestering agents, UV-ray absorbers, drugs, natural extracts such as animal and vegetable extracts, pigments, dispersing agents, flavors, etc., if desired, within the range which does not impair the effect of the present invention.
  • amino acids may include alanine, alginine, alginine hydrochloride, asparagine monohydrate, aspartic acid, citrulline, cysteine, cystine, glutamic acid, glutamic acid hydrochloride, glutamine, glycine, histidine, histidine hydrochloride, hydroxyproline, isoleucine, leucine, lysine, lysine hydrochloride, methionine, ornithine hydrochloride, proline, phenylalanine, serine, threonine, tryprophan, tyrosine, valine, dopa, o-aminobutyric acid, etc., which comprise a L-derivative, D-derivative, and DL-derivative.
  • Particularly preferred among the above are glycine, L-hydroxyproline, L-alanine, L-proline, and L-serine, and the metals for forming salts therewith may include sodium, potassium, potassium
  • all oil components generally employed in cosmetics, pharmaceuticals, etc., other than the above oil components can be used, and a broad range of from polar oils to non-polar oils can be used.
  • oil components may include hydrocarbon type oil components such as liquid paraffin, squalane, petrolatum, microcrystalline wax, etc.; ester oils such as isopropyl myristate, cetyl isooctanoate, glyceryl trioctanoate, etc.; silicone oils such as octamethyltetrasiloxane, decamethylpentasiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, etc.; high molecular weight silicones exhibiting soft rubbery state such as dimethylpolysiloxane, methylphenylpolysiloxane, terminal hydroxyl containing dimethylpolysiloxane, terminal hydroxyl containing methylphenylpolysiloxane (i.e., dimethylpolysiloxane containing a terminal hydroxyl group), etc.; lanolin, beeswax, olive oil, coconut oil, safflower oil, etc
  • oil-soluble and water-soluble substances or dispersible substances can be formulated within the range which does not impair the effect of the present invention.
  • NMF Natural Moisturizing Factor
  • components conventionally used can be formulated within the range which does not impair the effect of the present invention.
  • the aqueous phase component mucopolysaccharides such as sodium hyaluronate
  • organic acids and organic acid salts such as amino acids, amino acid salts, hydroxyacid salts, etc.
  • the oil phase component solid or semi-solid oil components such as petrolatum, lanolin, ceresine, silicone wax, microcrystalline wax, carunauba wax, candelilla wax, higher fatty acids, higher alcohols, etc.
  • fluid oil components such as squalane, liquid paraffin, ester oils, triglycerides, etc.
  • surfactants such as cationic surfactants, anionic surfactants, nonionic surfactants, etc.
  • drugs such as vitamin E, vitamin E acetate, etc.; styptics; antioxidants; preservative
  • the W/O type emulsion according to the first aspect of the present invention is prepared by utilizing the complex W/O emulsifying action of a conventional emulsifier and a water-swellable clay mineral, and the total amount of both functioning as the W/O emulsifier may be as small as 0.25 to 5% by weight, whereby the viscosity can be controlled by controlling the formulated amount or the ratio of the inner aqueous phase without the formulation of a solidifying agent such as wax, and an oil component with a high polarity, which could be formulated only with difficulty in the prior art, can be used, and accordingly, an excellent storage stability over a wide temperature range is obtained.
  • the W/O type emulsion of the present invention having these great advantages can be widely utilized in the wide fields of cosmetics and pharmaceuticals, etc.
  • the W/O type emulsion according to the second aspect of the present invention by utilizing an organic modified clay mineral formed from a water-swellable clay mineral, quaternary ammonium salt type cationic surfactant and a polyoxyalkylene modified organopolysiloxane as the emulsifier and gelling agent in the recipe, a good emulsifiability is exhibited even when the amount formulated is as small as 0.25 to 7% by weight, and by controlling the amount or the ratio of the inner aqueous phase or the outer oil phase, the viscosity can be controlled without formulating a large amount of a solidifying agent such as wax, etc.
  • a solidifying agent such as wax, etc.
  • an oil component with high polarity which could be formulated only with difficulty in the prior art, also can be used, and thus the emulsion has an excellent stability over a wide temperature range.
  • the use of the organic silicone resin as the oil phase component in the W/O type emulsion of the present invention ensures that the emulsion has a good water resistance and water repellency, and therefore, is able to store a substance to be maintained on the skin for a long period such as a drug, UV-ray absorber, humectant, etc.
  • the W/O type emulsion of the present invention having these great advantages can be widely utilized in fields such as cosmetics or pharmaceuticals, by making use of the specific features thereof.
  • the viscosity can be controlled without the formulation of a solidifying agent such as wax, etc., and by using a silicone oil, which could be formulated only with difficulty in the prior art, the inner phase can be a region bridging the region with water as the main component and the region with a polyhydric alcohol as the main component, and the composition also has an excellent storage stability over a wide temperature range.
  • the emulsified composition of the present invention suffers little change in viscosity due to temperature changes and has a high water repellency when coated on the skin; different from the case when thickened with a wax, etc.
  • the water- and polyhydric alcohol-in-oil type emulsified composition having these great advantages can be widely utilized in the fields of pharmaceuticals, cosmetics, paints, etc., by making use of the specific features thereof.
  • an organic modified mineral clay previously treated also may be employed, but if a control of the viscosity by controlling the formulation ratio of the water-swellable clay mineral and the quaternary ammonium salt type cationic surfactant is desired, the application range is broader if these components are formulated separately.
  • the method for preparing the emulsified composition of the present invention may be practiced by previously treating the water-swellable clay mineral with the quaternary ammonium salt type cationic surfactant and then formulating the oil components to effect thickening, followed by an emulsification of water and the polyhydric alcohol therein, or alternatively by adding the water-swellable clay mineral to the water and polyhydric alcohol phase to effect swelling and dispersion, followed by an emulsification by adding a homogeneous mixture prepared previously by introducing the quaternary ammonium salt type cationic surfactant and the polyoxyalkylene modified organopolysiloxane into the oil phase.
  • the components (1)-(6) were dispersed by mixing to prepare previously an oil phase, and a solution prepared by homogeneously dissolving the components (7) to (11) was then added gradually to the oil phase, with stirring by a disper, to obtain the desired moisture cream.
  • Example 1-2 Hand cream
  • the desired hand cream was obtained similarly as in Example 1-1.
  • the desired cosmetic base cream was obtained as in Example 1-1.
  • the components (1)-(8) were dissolved by mixing under heating at 70° C. to prepare an oil phase. Next, the components (9)-(12) were dispersed and mixed at 70° C. and then the mixture was gradually added, while stirring by a disper until mixed homogeneously, followed by cooling to obtain the desired hand cream.
  • Example 2-2 Milky lotion
  • the desired emulsion was obtained as in Example 2-1.
  • the desired pre-make-up milky lotion was obtained as in Example 2-2.
  • the desired sun screen cream was obtained as in Example 2-1.
  • This cream was obtained by replacing all of the amounts of the polyoxyalkylene modified organopolysiloxane, distearyldimethylammonium chloride, and smecton forming the organic modified clay mineral with sorbitan sesquioleate in the recipe in Example 2-1.
  • This cream was obtained by replacing all of the amount of the polyoxyalkylene modified organopolysiloxane with diglyceryl diisostearate in Example 2-1.
  • Example 2-4 and Comparative Example 2-3 were applied, and after swimming for 2 hours, the absorber was extracted with ethanol from the coated portion and measured by a spectrophotometer, and the residual percentage calculated by the ratio thereof before and after coating.
  • the Examples of the present invention has an excellent stability and water repellency, and the residual percentage of UV-rays absorber after swimming is high.
  • the desired moisture cream was obtained as in Example 2-1.
  • Examples 2-5 and 2-6 were found to have an excellent temperature stability and usability.
  • the mixture was emulsified by adding a solution obtained by mixing (1), (3) and (4), and heating. The mixture was then cooled to room temperature to obtain an emulsified composition.
  • the water- and polyhydric alcohol-in-oil type emulsified composition of the present invention is given an excellent stability by emulsifying well water and polyhydric alcohol with a silicone oil.
  • Example 3-1 the amount of Smectite in Example 3-1 was reduced from 1.5% to 1.0%, 0.5%, and 0.25%, to produce Examples 3-2, 3-3 and 3-4, and Comparative Example 3-6 contained no Smectite.
  • the relationships of the amounts with the viscosity in these Examples are shown in FIG. 1.
  • Examples 3-5 to 3-8 and Comparative Examples 3-7 and 3-8 are shown in Table 4, and Examples 3-9 to 3-12 and Comparative Example 3-9 are shown in Table 5.
  • Oil portion (B) was uniformly dispersed at 70° C. followed by gradually adding the uniformly dissolved aqueous phase (A) thereto, and then the desired cream was obtained by cooling.

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  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Colloid Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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US5196187A (en) * 1990-05-10 1993-03-23 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Cosmetic composition
US5216033A (en) * 1989-06-29 1993-06-01 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Water-in-oil transparent emulsion for the skin
WO1993021930A1 (en) * 1992-04-28 1993-11-11 Estee Lauder, Inc. Method of preparing a multiphase composition
US5262087A (en) * 1991-05-01 1993-11-16 Kose Corporation Water-in-oil type emulsified composition
US5310578A (en) * 1990-09-17 1994-05-10 Merck Patent Gesellschaft Deposition of cosmetically functional material onto pigments and fillers
US5468417A (en) * 1994-01-07 1995-11-21 Dow Corning Corporation Silicone containing VOC complaint paint remover
US5468477A (en) * 1992-05-12 1995-11-21 Minnesota Mining And Manufacturing Company Vinyl-silicone polymers in cosmetics and personal care products
WO1995034278A1 (en) * 1994-06-16 1995-12-21 Nuskin International, Inc. Sunscreen emulsions
US5505937A (en) * 1992-12-15 1996-04-09 Revlon Consumer Products Corporation Cosmetic compositions with improved transfer resistance
US5523091A (en) * 1993-02-23 1996-06-04 L'oreal Useful cosmetic or pharmaceutical water-in-oil emulsion
US5585108A (en) * 1994-12-30 1996-12-17 Nanosystems L.L.C. Formulations of oral gastrointestinal therapeutic agents in combination with pharmaceutically acceptable clays
EP0748622A1 (de) † 1994-12-16 1996-12-18 Shiseido Company Limited Lippenstift präparat
US5650139A (en) * 1991-12-26 1997-07-22 Kao Corporation Oil-based solid cosmetic composition
US5660819A (en) * 1990-12-28 1997-08-26 Nipon Unicar Company Limited Cosmetic formulations
US5665368A (en) * 1994-11-03 1997-09-09 Estee Lauder, Inc. Sprayable compositions containing dispersed powders and methods for using the same
US5725845A (en) * 1995-11-03 1998-03-10 Revlon Consumer Products Corporation Transfer resistant cosmetic stick compositions with semi-matte finish
US5800816A (en) * 1994-10-25 1998-09-01 Revlon Consumer Products Corporation Cosmetic compositions
US5882662A (en) * 1997-05-09 1999-03-16 Avon Products, Inc. Cosmetic compositions containing smectite gels
US6017546A (en) * 1993-07-06 2000-01-25 Dow Corning Corporation Water-in-volatile silicone emulsion gel cosmetic
US6039960A (en) * 1997-05-28 2000-03-21 E-L Management Corp. Water containing wax-based product
US6071503A (en) * 1995-11-07 2000-06-06 The Procter & Gamble Company Transfer resistant cosmetic compositions
US6086663A (en) * 1997-04-21 2000-07-11 Dow Corning Toray Silicone Co., Ltd. Surface modifier composition
US6139823A (en) * 1995-11-07 2000-10-31 The Procter & Gamble Company Transfer resistant cosmetic compositions
US6150425A (en) * 1997-07-17 2000-11-21 Shiseido Company, Ltd. O/W/O type multiphase emulsion
US6165450A (en) * 1999-05-03 2000-12-26 Em Industries, Inc. Sprayable sunscreen compositions
DE19939849A1 (de) * 1999-07-20 2001-01-25 Beiersdorf Ag Emulgatorfreie feindisperse Systeme vom Typ Wasser-in-Öl
US6190680B1 (en) * 1998-04-01 2001-02-20 The Nisshin Oil Mills, Ltd. Oily composition and process for producing the same
US6372830B1 (en) * 1998-09-14 2002-04-16 General Electric Company Water-in-oil type silicone emulsion compositions
US6406683B1 (en) 1995-11-07 2002-06-18 The Procter & Gamble Company Transfer resistant cosmetic compositions
US6410605B1 (en) * 1999-03-19 2002-06-25 Kao Corporation Process for preparing emulsion
US6428795B2 (en) * 1998-07-31 2002-08-06 Yoshimasa Miura Skin treatment composition
US20030064046A1 (en) * 1999-06-21 2003-04-03 Shiseido Company, Ltd. High internal aqueous phase water-in-oil type emulsion cosmetic composition
US6607734B1 (en) * 1999-10-15 2003-08-19 L'oreal Composition in the form of a water-in-oil emulsion containing fibers, and cosmetic use thereof
US6660277B1 (en) 1998-06-19 2003-12-09 Avon Products, Inc. Gel matrix non-emulsion composition containing two clay gels
US6683117B2 (en) * 2001-04-06 2004-01-27 Mizusawa Industrial Chemicals Ltd Oiliness agent and water-in-oil emulsion containing same
US20040142838A1 (en) * 2001-05-30 2004-07-22 Takaya Azuma Detergent composition for dry cleaning
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US6881415B1 (en) 1999-07-20 2005-04-19 Beiersdorf Ag Emulsifier-free finely dispersed water-in-oil type systems
US20050186166A1 (en) * 2004-02-23 2005-08-25 Patil Anjali A. Cosmetic compositions with silicone resin polymers
US7037511B1 (en) * 1999-08-21 2006-05-02 Beiersdorf Ag Hydrous cosmetic or pharmaceutical sticks
US20060110414A1 (en) * 2002-12-27 2006-05-25 Shiseido Co., Ltd. Oily skin preparation for external use
USRE39218E1 (en) 1994-09-30 2006-08-01 L'oreal Anhydrous and water-resistant cosmetic compositions
US7138128B2 (en) * 1998-11-19 2006-11-21 Beiersdorf Ag Preparations of the W/O emulsion type with an increased water content, and comprising cationic polymers
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US5985177A (en) * 1995-12-14 1999-11-16 Shiseido Co., Ltd. O/W/O type multiple emulsion and method of preparing the same
DE69732464T2 (de) * 1996-10-03 2006-05-11 Shiseido Co. Ltd. Äusserliches gelförmiges Hautpflegemittel
FR2771416A1 (fr) * 1997-11-25 1999-05-28 Rhodia Chimie Sa Utilisation de polysiloxanes comprenant des motifs polyethers et/ou des motifs amines comme agents anti-buee et formulations les comprenant
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US5145603A (en) * 1989-01-12 1992-09-08 Henkel Kommanditgesellschaft Auf Aktien Free-flowing, nonionic fat dispersion
US5216033A (en) * 1989-06-29 1993-06-01 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Water-in-oil transparent emulsion for the skin
US5196187A (en) * 1990-05-10 1993-03-23 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Cosmetic composition
AU636483B2 (en) * 1990-05-10 1993-04-29 Unilever Plc Cosmetic composition
US5310578A (en) * 1990-09-17 1994-05-10 Merck Patent Gesellschaft Deposition of cosmetically functional material onto pigments and fillers
US5660819A (en) * 1990-12-28 1997-08-26 Nipon Unicar Company Limited Cosmetic formulations
US5262087A (en) * 1991-05-01 1993-11-16 Kose Corporation Water-in-oil type emulsified composition
US5681551A (en) * 1991-12-26 1997-10-28 Kao Corporation Oil-based solid cosmetic composition
US5650139A (en) * 1991-12-26 1997-07-22 Kao Corporation Oil-based solid cosmetic composition
US5304334A (en) * 1992-04-28 1994-04-19 Estee Lauder, Inc. Method of preparing a multiphase composition
WO1993021930A1 (en) * 1992-04-28 1993-11-11 Estee Lauder, Inc. Method of preparing a multiphase composition
US5468477A (en) * 1992-05-12 1995-11-21 Minnesota Mining And Manufacturing Company Vinyl-silicone polymers in cosmetics and personal care products
US5725882A (en) * 1992-05-12 1998-03-10 Minnesota Mining And Manufacturing Company Vinyl-silicone copolymers in cosmetics and personal care products
US5505937A (en) * 1992-12-15 1996-04-09 Revlon Consumer Products Corporation Cosmetic compositions with improved transfer resistance
US5523091A (en) * 1993-02-23 1996-06-04 L'oreal Useful cosmetic or pharmaceutical water-in-oil emulsion
US6562324B1 (en) 1993-05-11 2003-05-13 Minnesota Mining And Manufacturing Polymers in cosmetics and personal care products
US6017546A (en) * 1993-07-06 2000-01-25 Dow Corning Corporation Water-in-volatile silicone emulsion gel cosmetic
US5468417A (en) * 1994-01-07 1995-11-21 Dow Corning Corporation Silicone containing VOC complaint paint remover
US5543136A (en) * 1994-06-16 1996-08-06 Nuskin International, Inc. Sunscreen emulsions
WO1995034278A1 (en) * 1994-06-16 1995-12-21 Nuskin International, Inc. Sunscreen emulsions
USRE39218E1 (en) 1994-09-30 2006-08-01 L'oreal Anhydrous and water-resistant cosmetic compositions
US5800816A (en) * 1994-10-25 1998-09-01 Revlon Consumer Products Corporation Cosmetic compositions
US20060088562A1 (en) * 1994-10-25 2006-04-27 Revlon Consumer Products Corporation Cosmetic compositions
US5911974A (en) * 1994-10-25 1999-06-15 Revlon Consumer Products Corporation Cosmetic compositions
US5965112A (en) * 1994-10-25 1999-10-12 Revlon Consumer Products Corporation Cosmetic compositions
US7005134B2 (en) 1994-10-25 2006-02-28 Revlon Consumer Products Corporation Cosmetic compositions
US7160550B2 (en) 1994-10-25 2007-01-09 Revlon Consumer Products Corporation Cosmetic compositions
US20070092468A1 (en) * 1994-10-25 2007-04-26 Revlon Consumer Products Corporation Cosmetic Compositions
US20040175345A1 (en) * 1994-10-25 2004-09-09 Revlon Consumer Products Corporation Cosmetic compositions
US5665368A (en) * 1994-11-03 1997-09-09 Estee Lauder, Inc. Sprayable compositions containing dispersed powders and methods for using the same
EP0748622B2 (de) † 1994-12-16 2012-08-29 Shiseido Company Limited Lippenstiftzusammensetzung
EP0748622A1 (de) † 1994-12-16 1996-12-18 Shiseido Company Limited Lippenstift präparat
US5585108A (en) * 1994-12-30 1996-12-17 Nanosystems L.L.C. Formulations of oral gastrointestinal therapeutic agents in combination with pharmaceutically acceptable clays
US5725845A (en) * 1995-11-03 1998-03-10 Revlon Consumer Products Corporation Transfer resistant cosmetic stick compositions with semi-matte finish
US6074654A (en) * 1995-11-07 2000-06-13 The Procter & Gamble Company Transfer resistant cosmetic compositions
US6340466B1 (en) 1995-11-07 2002-01-22 The Procter & Gamble Company Transfer resistant cosmetic compositions
US6406683B1 (en) 1995-11-07 2002-06-18 The Procter & Gamble Company Transfer resistant cosmetic compositions
US6071503A (en) * 1995-11-07 2000-06-06 The Procter & Gamble Company Transfer resistant cosmetic compositions
US6139823A (en) * 1995-11-07 2000-10-31 The Procter & Gamble Company Transfer resistant cosmetic compositions
US6086663A (en) * 1997-04-21 2000-07-11 Dow Corning Toray Silicone Co., Ltd. Surface modifier composition
US5882662A (en) * 1997-05-09 1999-03-16 Avon Products, Inc. Cosmetic compositions containing smectite gels
US6280753B1 (en) 1997-05-28 2001-08-28 E-L Management Corporation Water containing wax-based product
US6039960A (en) * 1997-05-28 2000-03-21 E-L Management Corp. Water containing wax-based product
US6150425A (en) * 1997-07-17 2000-11-21 Shiseido Company, Ltd. O/W/O type multiphase emulsion
US6190680B1 (en) * 1998-04-01 2001-02-20 The Nisshin Oil Mills, Ltd. Oily composition and process for producing the same
US6660277B1 (en) 1998-06-19 2003-12-09 Avon Products, Inc. Gel matrix non-emulsion composition containing two clay gels
US6428795B2 (en) * 1998-07-31 2002-08-06 Yoshimasa Miura Skin treatment composition
US6372830B1 (en) * 1998-09-14 2002-04-16 General Electric Company Water-in-oil type silicone emulsion compositions
US7138128B2 (en) * 1998-11-19 2006-11-21 Beiersdorf Ag Preparations of the W/O emulsion type with an increased water content, and comprising cationic polymers
US6410605B1 (en) * 1999-03-19 2002-06-25 Kao Corporation Process for preparing emulsion
US6165450A (en) * 1999-05-03 2000-12-26 Em Industries, Inc. Sprayable sunscreen compositions
US6841163B2 (en) * 1999-06-21 2005-01-11 Shiseido Company, Ltd. High internal aqueous phase water-in-oil type emulsion cosmetic composition
US20030064046A1 (en) * 1999-06-21 2003-04-03 Shiseido Company, Ltd. High internal aqueous phase water-in-oil type emulsion cosmetic composition
DE19939849A1 (de) * 1999-07-20 2001-01-25 Beiersdorf Ag Emulgatorfreie feindisperse Systeme vom Typ Wasser-in-Öl
US6881415B1 (en) 1999-07-20 2005-04-19 Beiersdorf Ag Emulsifier-free finely dispersed water-in-oil type systems
US7037511B1 (en) * 1999-08-21 2006-05-02 Beiersdorf Ag Hydrous cosmetic or pharmaceutical sticks
US6607734B1 (en) * 1999-10-15 2003-08-19 L'oreal Composition in the form of a water-in-oil emulsion containing fibers, and cosmetic use thereof
US6683117B2 (en) * 2001-04-06 2004-01-27 Mizusawa Industrial Chemicals Ltd Oiliness agent and water-in-oil emulsion containing same
US7125831B2 (en) * 2001-05-30 2006-10-24 Nof Corporation Detergent composition for dry cleaning comprising a cyclic polysiloxane and a polyether modified silicone
US20040142838A1 (en) * 2001-05-30 2004-07-22 Takaya Azuma Detergent composition for dry cleaning
US20060110414A1 (en) * 2002-12-27 2006-05-25 Shiseido Co., Ltd. Oily skin preparation for external use
US8062671B2 (en) * 2002-12-27 2011-11-22 Shiseido Co., Ltd. Oily skin preparation for external use
US20070166257A1 (en) * 2003-01-17 2007-07-19 Balanda Atis Long wear cosmetic composition
US8323628B2 (en) 2003-01-17 2012-12-04 L'oreal Long wear cosmetic composition
US20080207733A1 (en) * 2003-08-05 2008-08-28 Carlos Manuel Miyares Cao Composition for the Treatment of Vitiligo
DE10343851A1 (de) * 2003-09-23 2005-04-14 Beiersdorf Ag Sprühbare kosmetische Formulierung
US7879779B2 (en) * 2004-01-09 2011-02-01 Shiseido Co., Ltd. Oil-cleansing composition
US20080293603A1 (en) * 2004-01-09 2008-11-27 Shiseido Co., Ltd. Oil-Cleansing Composition
US20080050328A1 (en) * 2004-02-23 2008-02-28 Revlon Consumer Porducts Corporation Cosmetic Compositions with Silicone Resin Polymers
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EP0331833A1 (de) 1989-09-13
EP0331833B1 (de) 1992-07-29
JPH01180237A (ja) 1989-07-18
DE3873313D1 (de) 1992-09-03
JP2657504B2 (ja) 1997-09-24
DE3873313T2 (de) 1992-12-24

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